Methods for selective deposition on silicon-based dielectrics

Abstract

Methods of selectively depositing a film on a hydroxide terminated surface relative to a hydrogen terminated surface are described. The hydrogen terminated surface is exposed to a nitriding agent to form an amine terminated surface which is exposed to a blocking molecule to form a blocking layer on the surface. A film can then be selectively deposited on the hydroxide terminated surface.

What is claimed is: 
     
       1. A method comprising:
 exposing a substrate having a first surface with hydrogen terminations and a second surface with hydroxide terminations to a nitriding agent to form an amine terminated first surface; and 
 exposing the amine terminated first surface to a blocking molecule to form a blocking layer on the first surface. 
 
     
     
       2. The method of  claim 1 , wherein the first surface comprises silicon and the second surface comprises a silicon dielectric. 
     
     
       3. The method of  claim 1 , wherein the nitriding agent comprises one or more of ammonia, hydrazine or plasmas thereof. 
     
     
       4. The method of  claim 1 , wherein the blocking molecule comprises one or more of a carboxylic acid, acyl halide, ketone, anhydride, alcohol or aldehyde. 
     
     
       5. The method of  claim 4 , wherein the blocking molecule has in the range of about 1 to about 20 carbon atoms. 
     
     
       6. The method of  claim 5 , wherein the blocking molecule has in the range of about 6 to about 20 carbon atoms. 
     
     
       7. The method of  claim 1 , wherein the blocking molecule comprises undecanal. 
     
     
       8. The method of  claim 1 , further comprising selectively depositing a film on the second surface. 
     
     
       9. The method of  claim 8 , further comprising removing the blocking layer from the first surface after depositing a layer on the second surface. 
     
     
       10. The method of  claim 9 , wherein removing the blocking layer comprises exposing the blocking layer to an oxidizer. 
     
     
       11. The method of  claim 10 , wherein the oxidizer comprises one or more of oxygen plasma, ozone, high temperature oxygen anneal, peroxide or water. 
     
     
       12. The method of  claim 8 , wherein the blocking layer is not removed from the first surface after depositing a layer on the second surface. 
     
     
       13. A method of depositing a film comprising:
 providing a substrate comprising a first material having a first surface with hydrogen terminations and a second material having a second surface with hydroxyl terminations; 
 exposing the substrate to a nitriding agent comprising a species that reacts with the hydrogen terminations of the first surface to form an amine terminated first surface; and 
 exposing the amine terminated first surface to a blocking molecule to form a blocking layer on the first surface. 
 
     
     
       14. The method of  claim 13 , wherein the first surface comprises silicon and the second surface comprises a silicon dielectric. 
     
     
       15. The method of  claim 13 , wherein the nitriding agent comprises one or more of ammonia, hydrazine or plasmas thereof. 
     
     
       16. The method of  claim 13 , wherein the blocking molecule comprises one or more of a carboxylic acid, acyl halide, ketone, anhydride, alcohol or aldehyde. 
     
     
       17. The method of  claim 16 , wherein the blocking molecule has in the range of about 6 to about 20 carbon atoms. 
     
     
       18. The method of  claim 13 , wherein the blocking molecule comprises undecanal. 
     
     
       19. The method of  claim 13 , further comprising selectively depositing a film on the second surface. 
     
     
       20. A method of depositing a film comprising:
 providing a substrate comprising a first material comprising silicon having a first surface with hydrogen terminations and a second material comprising silicon oxide having a second surface with hydroxyl terminations; 
 exposing the substrate to a nitriding agent comprising ammonia that reacts with the hydrogen terminations of the first surface to form an amine terminated first surface; and 
 exposing the amine terminated first surface to a blocking molecule comprising undecanal to form a blocking layer on the first surface; and 
 selectively depositing a film on the second surface.